Substituted sulfonylglycolic acid anilides

ABSTRACT

New and valuable N-substituted sulfonylglycolic acid anilides and a process for controlling the growth of unwanted plants with these compounds.

United States Patent Ruhr et al. Feb. 11, 1975 SUBSTITUTED SULFONYLGLYCOLIC ACID [56] References Cited ANlLlDES UNITED STATES PATENTS [75] Inventors: Wolfgang Rohr, Mannheim; 3.536.721 10/1970 Soong et a1. 260/456 A X Adolf Fischer, Mutterstadt, both of Germany Primary Examiner-Leon Zitver [73] Assignee: Badische Anilin-& Soda-Fabrik N' Aktiengeseuschaft, Ludwigshafenl Attorney, Agent, or Firm-Johnston, Ken], Thompson Rhine, Germany Shumeff [22] Filed: Nov. 29, 1972 211 App]. No.: 310,640 [57] ABSTRACT New and valuable N-subsmuted sulfonylglycohc acld [301 Foreign Application Priority Data anilides and a process for controlling the growth of Dec 6 I97] (erm m 7160380 unwanted plants with these compounds.

y 1 6 Claims, No Drawings [52] [1.8. Cl 260/456 A, 424/303, 71/103 [51] Int. Cl. C07c 143/24, C07c 143/38 [58] Field of Search 260/456 A SUBSTITUTED SULFONYLGLYCOLIC ACID ANILIDES The present invention relates to new and valuable N- substituted sulfonylglycolic acid anilides and their use as herbicides.

It is known to use substituted acid anilides, e.g., chloroacetic acid-N-isopropylanilide, chloroacetic acid-N- propargylanilide and chloracetic acid-N- isobutynylanilide as herbicides. However, their action is unsatisfactory.

We have now found that N-substituted sulonylglycolic acid anilides of the formula where R denotes alkyl, cycloalkyl, haloalkyl, aralkyl, alkenyl, or haloalkenyl, or phenyl which may be substituted by alkyl, haloalkyl, alkoxy, halogen or nitro, R denotes phenyl which may besubstituted by alkyl, and R denotes alkyl of more than 2 carbon atoms, cycloalkyl, alkenyl or alkynyl, have a good herbicidal action. R may for instance have the following meanings: methyl, chloromethyl, ethyl, 2-chloroethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, benzyl, vinyl, allyl, butenyl, pentenyl, hexenyl, phenyl, 4-methylphenyl, 4-chlorophenyl, 4-bromophenyl, 4-nitrophenyl, 4- fluorophenyl, 4idophenyl, 4-ethylphenyl, 2-

nitrophenyl, 3-nitrophenyl, 3,4-dichlorophenyl, etc.

R may for instance have the following meanings:

phenyl, 2-methylphenyl, 3-methylpheny1, 4- methylphenyl, Z-ethylphenyl, 4-ethylphenyl, 2,6- dimethylphenyl, 2,6-diethylphenyl, 2,5- dimethylphenyl, 3,5-dimethylphenyl, 3,4- dimethylphenyl, 2,4-dimethylphenyl, 2,3 dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,5-

trimethylphenyl, 4-isopropylphenyl, 2-isopropylphenyl, 2'methyl-6-ethy1phenyl, 2,6-diisopropylphenyl, etc.

R may for instance denote the following radicals: npropyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, allyl, butenyl, pentenyl, hexenyl, propargyl, butynyl, pentynyl and hexynyl.

The compounds of the invention may be prepared by reacting a substituted glycolic acid anilide with a substituted sulfonyl chloride in the presence of an acid acceptor such as triethylamine.

The preparation of the compounds of the invention is illustrated in the following examples.

EXAMPLE 1 Preparation of acid-(N-butyn-l-yl-3)anilide At 0C and over a period of minutes, a solution of 21 parts by weight of methanesulfochloride in 26 parts by weight of dichloromethane was added to a solution of 30.5 parts by weight of N-butyn-1-yl-3-glycolic acid anilide and 27.6 parts of triethylamine in 920 parts by weight of dichloromethane. After 45 minutes the reaction mixture was washed with ice water, with cold 5 percent hydrochloric acid and subsequently with cold saturated sodium bicarbonate solution. The organic phase was dried with magnesium sulfate and concentrated in vacuo. During cooling the oily residue crystallized upon asmall amount of ether being added. The

O-methylsulfonylglycolic crude product was recrystallized from ether; melting point: 58 to 60C.

The compound has the following structural formula:

The following compounds for instance may be prepared analogously:

O-methylsulfonylglycolic acid-(N-propargyU-anilide O-ethylsulfonylglycolic acid-(N-propargyl)-ani1ide O-propylsulfonylglycolic acid-(N-propargyl)-anilide O-isopropylsulfonylglycolic acid-(N-propargyl)- anilide O-n-butylsulfonylglycolic acid-(N-propargyl)-anilide O-ethylsulfonylglycolic acid-(N-butynl -yl-3 anilide, m.p. 76 to 78C O-propylsulfonylglycolic anilide, m.p. 50 to 52C O-isopropylsulfonylglycolic ani1ide,m.p. 83 to 85C O-n-butylsulfonylglycolic anilide, m.p. 69 to 71C O-cyclohexylsulfonylglycolic anilide, m.p. 99 to 100C O-chloromethylsulfonylglycolic acid-( N-butynl -yl- 3)-anilide, m.p. 80 to 81C O-methylsulfonylglycolic acidl-(N-3-methylbutynl-yl-3)-anilide, m.p. 89 to 90C O-ethylsulfonylglycolic acid-(N-3-methylbutyn-l-yl- 3)-anilide O-propylsulfonylglycolic l-yl-3)-anilide O-isopropylsulfonylglycolic acidl-(N-3-methylbutyn- 1-yl-3 )-anilide O-n-butylsulfonylglycolic 1-yl-3 )-anilide O-phenylsulfonylglycolic anilide, m.p. 86 to 87C O-4-methylphenylsulfonylglycolic l-yl-3)-anilide, m.p. 67 to 69C O-4 -chloropheny1sulfonylglycolic 1-yl-3)-anilide, oil O-methylsulfonylglycolic acid-(N-isopropyl)-anilide,

m.p. 92 to 93C O-methylsulfonylglycolic acid-(N'isobuty1)-anilide,

m.p. 70 to 71C O-methylsulfonylglycolic acid-(N-tert-butyl)-anilide O-ethylsulfonylglycolic acid-(N-isopropyl)-anilide,

m.p. 60 to 61C O-ethylsulfonylglycolic acid-(N-iisobutyl)-anilide O-ethylsulfonylglycolic acid-(N-tert-butyl) anilide O-propylsulfonylglycolic acid-(N-isopropyl)-anilide,

m.p. 56 to 57C O-propylsulfonylglycolic acid-(N-isobutyl)-anilide O-isopropylsulfonylglycolic acid-(N-isopropyl)- anilide, m.p. 60 to 62C O-phenylsulfonylglycolic acid-(N-isopropyl)-anilide acid-(N3-methylbutynacid-(N-3-methylbutynacid-( N-butynl -yl-3 acid-(N-butynacid-(N-butyn- O-4-methylphenylsulfonylglycolic acid-(N- isopropyl)-anilide O-4-chlorophenylsulfonylglycolic acid-(N- isopropylyanilide O-phenylsulfonylglycolic acid-(N-propargyl)-ani1ide O-4-methylphenylsulfonylglycoli-c acid-(N- propargyl)-ani1ide 3 O-4-chlorophenylsulfonylglycolic propargyl)-anilide O-methylsulfonylglycolic acid-(N-allyl)-anilide O-ethylsulfonylglycolic acid-(N-allyl)-anilide O-propylsulfonylglycolic acid-(N-allyl)-anilide O-n-butylsulfonylglycolic acid-(N-al1yl)-anilide O-phenylsulfonylglycolic acid-(N-allyl)-anilide O-4 methylphenylsulfonylglycolic acid-(N-allyl)- anilide O-4-chlorophenylsulfonylglycolic anilide O-butylsulfonylglycolic m.p. 76 to 78C O-pentylsulfonylglycolic acid(N-isopropyl)-anilide,

m.p. 50 to 52C O-cyclohexylsulfonylglycolic anilide, m.p. 110 to 112C O-benzylsulfonylglycolic acid(N-isopropyl)-anilide,

m.p. 107 to 108C O-isopropylsulfonylglycolic anilide, m.p. 55 to 56C O-butylsulfonylglycolic acid(N-sec-butyl)-anilide,

m.p. 44 to 46C O-pentylsulfonylglycolic anilide, m.p. 49 to 50C O-benzylsulfonylglycolic anilide, m.p. 65 to 66C. The corresponding O-sulfonyl-N-alkenyland O-sulfonyl-N-alkylglycolic acid anilides may be prepared from suitable O-sulfonyl-N-alkynylglycolic acid anilides by partial or complete hydrogenation of the carbon-carbon triple bond.

EXAMPLE 2 Preparation of acid-(N-buten-l-yl-3)-anilide 1 part by weight of catalyst (0.7 percent by weight palladium on calcium carbonate, with added zinc) was added to a solution of 28.1 parts by weight of O-methylsulfonylglycolic acid-(Nbutynl-yl-3)-anilide in 180 parts by weight of ethyl acetate, and hydrogenation carried out until 2,350 parts by volume of hydrogen had been absorbed at room temperature and 0.02 atmosphere gauge. The catalyst was then separated, the solution evaporated to dryness in vacuo and the residue recrystallized from ether; m.p.i 54 to 55C.

Similarly, O-methylsulfonylglycolic acid-(N-secbutyl)-anilide (m.p.: 68 to 70C) may be obtained by complete hydrogenation employing a palladium on activated carbon percent) catalyst.

The agents according to the invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a time distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbons having boiling points higher than 150C, e.g., tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150C and having one or more than one functional group, e.g., the keto group, the ether group, the ester group or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component ofa heterocyclic ring, may be used as spray liquids. I

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by addacid(N-allyl acid-( N-isopropyl)-anilide,

acid( N-isopropyl acid-( N-sec-butyl O-methylsulfonylglycolic ing water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e.g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent. Oils or adhering agents may also be added.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g., kieselguhr, talc, clay or fertilizers.

Granules may be prepared by blending with solid carriers.

EXAMPLE 3 Loamy sandy soil was filled into pots and sown with Zea mays, Soja hispida, Gossypium hirsutum, Echinochloa crusgalli, Setaria spp., Poa trivialis, Lolium multiflorum and Sinapis arvensis.

The soil was then treated with 2 kg per hectare of O-methylsulfonylglycolic acid( N-butyn- 1 -yl-3 )-anilide (I), 2 kg per hectare of O-methylsulfonylglycolic acid(N-secbutyl)-anilide (II) and, for comparison, with 2 kg per hectare of N-propargyl-achloroacetanilide (111) and 2 kg per hectare of N- butyn-(l)-yl-(3)-chloroacetic acid anilide (Vll), each active ingredient being dispersed in 500 liters of water per hectare.

After 4 to 5 weeks it was observed that I and 11 had a stronger herbicidal action on the broadleaved and grassy weeds than 111 and VII, and combined with the same good crop plant compatibility.

The results of this experiment are given below:

0 no damage complete destruction The action of the following compounds corresponds to that of I and 11 in this experiment: O-methylsuflonylglycolic acid-(N-isopropyl)-anilide O-methylsulfonylglycolic acid(N-isobutyl)-anilide.

EXAMPLE 4 The plants Zea mays, Triticum aestivum, Echinochloa crusgalli, Setaria spp., and Panicum spp. were treated at a growth height of from 5 to 15 cm with 3 kg per hectare of each of the following active ingredients, each being dispersed in 500 liters of water per hectare: O-methylsulfonylglycolic acid( N-butyn-1-yl-3)-anilide (l); O-methylsulfonylglycolic acid(N-sec-butyl)- anilide (I1); and, for comparison, N-propargyl-achloroacetanilide (lll); N-butyn-( l )-yl-(3 )-achloroacetanilide (V11).

After 3 to 4 weeks it was ascertained that active ingredients l and 11 had a stronger herbicidal action on the broadleaved and grassy weeds than 111 and VII, combined with the same or superior crop plant compatibility.

The results of this experiment are given below:

-Continued I II III VII IV V VI VII Gossypium hirsutum 0 0 25 25 fh 0 0 O 0 Beta vulgaris l0 0 20 30 Tmlcum aesuvum O 0 30 5 Ecinochloa crus-galli 9O 85 70 80 Echinochloa crus-galll 95 80 65 70 pon annua 90 9O 30 6o Senna PP 80 70 55 50 Panicum spp. 95 90 65 70 q pp- 85 75 60 Avena fatua s0 s0 40 45 Matricaria chamomllla 90 80 6O 70 0 no damage 0 no damage 100 complete destruction 1O t dcslwctivn The action of the following compounds corresponds to that of l and II above: O-methylsulfonylglycolic EXAMPLE 7 acid-(N-isopropyl)-anilide acid-( N-isobutyl )-anilide.

EXAMPLE 5 Loamy sandy soil was filled into pots and sown with Zea mays, Soja hispida, Gossypium hirsutum, Beta vulgaris, Echinochloa crus-galli, Setaria spp., Poa trivialis, Bromus tectorum and Alopecurus myosuroides.

The soil prepared in this manner was then treated with 2 kg per hectare of each of the following active ingredients, each being dispersed in 500 liters of water per hectare: O-ethysulfonylglycolic acid-(N-butyn- 1-yl-3)-anilide (IV); O-n-butylsulfonylglycolic acid-(N butyn-l-yl-3)-anilide' (V); and, for comparison, N-isopropyl-a-chloroacetanilide (VI); 'N-butyn- (l )-yl-(3 )-a-chloroacetanilide (VII).

After 4 to 5 weeks it was ascertained that active in- O-methylsulfonylglycolic gredients IV and V had a stronger herbicidal action than VI and VII, combined with the same or superior crop plant compatibility.

The results are given below:

The plants Zea mays, Gossypium hirsutum, Beta vulgaris, Echinochloa crus-galli, Poa annua, Panicum spp. and Avena fatua were treated at a growth height of from 3 to 15 cm with 4 kg per hectare of each of the IV VI VII Zea mays O 0 5 90 parts by weight of compound I is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 8 20 parts by weight of compound II is dissolved in a mixture consisting of parts by weight of xylene. 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N- monoethanolamide. 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02 percent by weight of the active ingredient.

EXAMPLE 9 20 parts by weight of compound. IV is dissolved in a mixture consisting of 40 parts by weight of cyclohexa' none, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02 percent by weight of the active ingredient.

EXAMPLE 10 20 parts by weight of compound V is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02 percent by weight of the active ingredient.

EXAMPLE 1 1 20 parts by weight of compound I is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalenea-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1 percent by weight of the active ingredient.

EXAMPLE l2 3 parts by weight of compound II is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3 percent by weight of the active ingredient.

EXAMPLE 13 30 parts by weight of compound IV is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 14 In the greenhouse, loamy sandy soil was filled into pots and sown with Zea mays, Gossypium hirsutum, Glycine hispida, Beta vulgaris, Brassica oleracea, Echinochloa crus-galli, Setaria faberii, Alopecurus myosuroides and Eleusine indica. The soil prepared in this manner was then treated with 1 and 2 kg per hectare of each of the following active ingredients, each being emulsified in 500 liters of water per hectare:

l O-methylsulfonylglycolic acid-[N-butyn-( 1 )-yl- (3 )]-anilide; ll O-n-butylsulfonylglycolic acid-[N-butyn-( 1 )-yl- (3)]-anilide; llI O-phenylsulfonylglycolic acid-[N-butyn-(l)-yl- (3)]-anilide; IV O-p-methylphenylsulfonylglycolic acid-[N-butyn- (l)-yl-(3 )]-anilide; V O-methylsulfonylglycolic acid-(N-methyl)-anilide. After 4 to 5 weeks it was ascertained that active ingredients l to 1V had a stronger herbicidal action than comparative agent V, combined with the same excellent crop plant compatibility.

The results of this experiment are given below:

1 11 Ill Zea mays 0-10 0-10 10 Glycine hispida 0 0 5 Gossypium hirsutum 0 0 0 Beta vulgaris 0 0 0 Oryza sativa 0-10 0-10 0-10 Triticum aestivum 0-10 0-10 0-10 Hordeumvulgare 0-10 0-10 0-10 Eleusine indica 90-100 90-100 60-70 Echinochloa crus-galli 90-100 100 -50 Setaria faberii 90-100 100 Panicum virgatum 90-100 100 I 60 Digitaria sanguinalis 90-100 90-100 60-70 Alopecurus myosuroides 90-100 100 60-70 Poa annua 100 100 -80 0 no damage 100 complete destruction The action of the following compounds corresponds to that of l and H in this example: O-phenylsulfonylglycolic acid-[N-butyn-( l )-yl-(3 ]-anilide O-pmethylphenylsulfonylglycolic acid-[N-butyn-( 1 )-yll 11 Ill kg/ha 1 2 1 2 1 2 Zea mays 0 0 0 0 0 0 Gossypium hirsutum 0 0 0 0 0 0 Soja hispida O 0 O O O 0 Beta vulgaris 0 0 0 0 0 0 Brassica oleracea O 0 O 0 O 0 Echinochloa crus-galli 90-100 100 100 100 90 90-100 Setaria faberii 90-100 100 100 100 90 90-100 Alopecurus myosuroides 90 60-70 80 Eleusine indica 90-100 100 90-100 100 90 90-100 IV V kg/ha l 2 1 2 Zea mays 0 0 0 0 Gossypium hirsutum 0 0 0 0 Soja hispida 0 0 0 0 Beta vulgaris 0 0 O 0 Brassica oleracea 0 0 0 0 Echinochloa crus-galli 90-100 100 70-80 90 Setaria faberii 90-100 100 70 80-90 Alopecurus myosuroides 80-90 90-100 50-60 70-80 Eleusine indica 90-100 100 70-80 80-90 0 no damage 100 complete destruction EXAMPLE 15 In the greenhouse, the plants Zea mays, Glycine hispida, Gossypium hirsutum, Beta vulgaris, Oryza sativa, Triticum aestivum, Hordeum vulgare, Eleusine indica, Echinochloa crus-galli, Setaria faberii, Panicum virgatum, Digitaria sanguinalis, Alopecurus myosuroides and Poa annua were treated at a growth height of the 60 (3)]-anilide.

We claim: 1. A N-substituted sulfonylglycolic acid anilide of the formula 8 2 l R SO OCH C 

1. A N-SUBSTITUTED SULFONYLGLYCOLIC ACID ANILIDE OF THE FORMULA
 2. O-methylsulfonylglycolic acid-(N-butyn-1-yl-3)-anilide.
 3. O-ethylsulfonylglycolic acid-(N-butyn-1-yl-3)-anilide.
 4. O-n-propylsulfonylglycolic acid-(N-butyn-1-yl-3)-anilide.
 5. O-isopropylsulfonylglycolic acid-(N-butyn-1-yl-3)-anilide.
 6. O-n-butylsulfonylglycolic acid-(N-butyn-1-yl-3)-anilide. 